This invention relates to electrode materials for energy storage devices, notably electrochemical cells and batteries and, more particularly, non-aqueous lithium cells and batteries. Lithium cells and batteries are of particular use for powering a wide range of applications such as portable electronic devices (for example, cell phones and laptop computers), medical-, space-, aeronautic- and defense-related devices and in transportation applications, such as hybrid-electric- and all-electric vehicles.
This invention relates to electrode materials for energy storage devices, notably electrochemical cells and batteries and, more specifically, non-aqueous lithium cells and batteries. More specifically, in one aspect, the invention relates to electrode materials synthesized within an enclosed reaction chamber. The method of synthesis makes use of an autogenic pressure reactor in which one or more, dry, solvent-free chemical precursor powders are dissociated and reacted in the enclosed chamber at elevated temperature, thereby creating self-generated pressure within the chamber. The reactor is designed to operate typically up to a maximum working pressure of about 2000 pounds per square inch and a maximum temperature of about 800° C. Reaction parameters such as heating rate, temperature, time, reactant concentration, stoichiometry, pressure, and atmosphere (either oxidizing, reducing or inert) can be controlled to fabricate a wide range of electrode materials with various compositions, morphologies, particle shape and size, with either nano- or micron sized dimensions. The carbon-containing materials prepared according to the invention include both stoichiometric and defect materials with respect to their composition and their atomic, cationic or anionic sites.
Furthermore, the autogenic pressure reactor and method can produce, in situ, a variety of novel, unique ‘core-shell’ electrode materials. For example, the methods of this invention can produce core-shell materials with a metal, metal alloy, metalloid, metal oxide, metal phosphate or metal silicate core and an outer shell, coating or environment, for example, a carbon shell, coating or environment providing improved electronic and/or ionic conductivity on and between electrode particles. This can be particularly important when insulating anode and cathode products, such as TiO2 and LiFePO4, respectively, are fabricated. Spherical carbon particles, and rounded carbon particles with distorted shapes such as prolate or oblate shapes, carbon nanotubes or mixtures of shapes, that can be used either as an active anode material or as a current collector for either the anode or cathode, or both, can also be produced by autogenic reactions.
A particularly important embodiment of this invention is that these carbon materials are preferably heated after autogenic synthesis to elevated temperatures above 1000° C. in an inert atmosphere, such as under vacuum or argon gas, to improve their electrochemical properties. The electrode materials produced by the reactor have particular application in energy storage devices such as primary and secondary (rechargeable) batteries including, for example, lithium polymer batteries, lithium sulfur batteries and most notably lithium-ion batteries that are used for powering a broad range of devices, such as portable electronics (for example, cell phones and laptop computers), medical, space, aeronautical and defense-related devices, as well as hybrid-electric, plug-in hybrid-electric, and all-electric vehicles.
A lithium- or lithium-ion electrochemical cell is described herein, which comprises a lithium-containing cathode, an anode, and a non-aqueous lithium-containing electrolyte therebetween; wherein one or more of the anode and/or the cathode comprises at least one particulate carbon material comprising nanoparticles of the surface of individual carbon particles, wherein the nanoparticles are elected from one or more of (a) a metal oxide or sulfide comprising one or more metal ions selected from the group consisting of Ti, Fe, Mn, Co, Ni, Mo, W, In, and Sn; (b) one or more metals selected from the group consisting of Ti, Fe, Co, Mg, Al, Ga, In, and Sn; and (c) one or more metalloid selected from the group consisting of B, Si, Ge, and Sb. Preferably, the carbon particles comprise generally spherical carbon particles, rounded particles, prolate spheroid particles, oblate-shaped particles, nanotube particles, or a combination thereof. In one preferred embodiment, the carbon particles comprise generally spherical microparticles having a size in the range of about 1 to about 5 microns in diameter. Preferably, the nanoparticles are deposited on the surface of the carbon particles by sonication of a slurry of carbon particles in a solvent (e.g., an alcohol) in the presence of a metal compound (e.g., a compound such as a metal halide, a metal, carboxylate, a metal alkoxide, a metal nitrate, a metal phosphate, a metal sulfate, and the like, excluding elemental metals and alloys thereof), a metalloid compound (e.g., a compound such as a metalloid halide, a metalloid, carboxylate, a metalloid alkoxide, a metalloid nitrate, a metalloid phosphate, a metalloid sulfate, and the like, excluding elemental metalloids and alloys thereof), or a combination thereof, optionally under an atmosphere.
In some preferred embodiments, the nanoparticles comprise elemental Sn, SnO2, elemental Sb, SnO2 and elemental Sb, or elemental Sn and elemental Sb.
In another embodiment, the carbon material comprises carbon nanotubes with Fe nanoparticles on the surface thereof.
In one particular embodiment, the present invention provides a lithium or lithium-ion electrochemical cell comprising a cathode, an anode, and a non-aqueous lithium-containing electrolyte therebetween, wherein one or more of the anode and/or the cathode comprises at least one particulate carbon-containing material selected from the group consisting of: (a) a particulate metal oxide/carbon composite material, optionally in combination with Li ions, the metal oxide or sulfide comprising one or more ions selected from the group consisting of Ti, Fe, Mn, Co, Ni, Mo, W, In, and Sn, (b) a particulate metal/carbon composite material comprising one or more metal selected from the group consisting of Ti, Fe, Co, Mg, Al, Ga, In, and Sn (preferably a metal that can alloy with Li such as Mg, Al, Ga, In, and Sn), (c) a particulate metalloid/carbon composite material comprising one or more metalloid that can alloy with Li selected from the group consisting of B, Si, Ge, and Sb, (d) a particulate metal phosphate/carbon composite material, optionally in combination with Li ions, wherein the metal phosphate comprises one or more ions selected from the group consisting of Ti, V, Mn, Ni, and Co, and (e) a particulate carbon material comprising rounded carbon particles that preferably, but not exclusively, are selected from the group consisting of carbon spheres, prolate-shaped spheroids, oblate-shaped spheroids, and carbon nanotubes. The particulate carbon-containing material is prepared by heating one or more precursor materials in a sealed autogenic pressure reactor at a temperature and for a period of time sufficient to dissociate the one or more precursor material into at least one gaseous component and thereby generate a pressure sufficient for components of the dissociated precursor material to combine and form the particulate carbon-containing material; wherein the combined amount and chemical composition of each precursor material in the reactor is sufficient to form the particulate carbon-containing material.
In another aspect, the present invention provides a method of fabricating rounded carbon particles suitable for use in an electrochemical cell. The method comprises heating one or more precursor materials in a sealed autogenic pressure reactor at a temperature and for a period of time sufficient to dissociate the one or more precursor material into at least one gaseous component and thereby generate a pressure sufficient for components of the dissociated precursor material to combine and form the particulate carbon-containing material. The combined amount and chemical composition of each precursor material in the reactor is selected so as to be sufficient to form the particulate carbon-containing material. The method further includes isolating the rounded carbon particles from the reactor, generally after cooling the reactor (e.g., to ambient room temperature), and subsequently annealing the isolated rounded particles under an inert atmosphere at a temperature in the range of about 1000 to about 3000° C. (preferably about 2000 to about 3000° C., more preferably about 2400 to about 3000° C.). The rounded carbon particles preferably, but not exclusively, are selected from the group consisting of carbon spheres, prolate-shaped carbon spheroids, oblate-shaped carbon spheroids, carbon nanotubes, and a combination thereof. Rounded carbon particles prepared by this method are also encompassed by the present invention. Preferably, the rounded particles exhibit a Raman spectrum characterized by bands centered at about 1300 to 1350 cm−1, at about 1550 to 1600 cm−1 and at about 1600 to 1650 cm−1.
In addition, the present invention provides a method for fabricating a carbon-coated particulate metal oxide, metal phosphate, metal, or metalloid material suitable for use in an electrode of an electrochemical cell. The method comprises heating one or more precursor material in a sealed autogenic pressure reactor at a temperature and for a period of time sufficient to dissociate the one or more precursor material into at least one gaseous component and thereby generate a pressure sufficient for components of the dissociated precursor material to combine and form the carbon-coated particulate material. Carbon-coated particulate metal oxide, metal phosphate, metal, and metalloid materials prepared by this method also form part of the present invention.
Also described herein is a method of fabricating a particulate carbon material comprising nanoparticles on the surface of individual carbon particles. The method comprises sonicating a slurry of carbon particles in a solvent (e.g., an alcohol) in the presence of a metal compound, a metalloid compound, or a combination thereof, optionally under an atmosphere, as described herein. The nanoparticles are selected from one or more of (a) a metal oxide or sulfide comprising one or more metal ions selected from the group consisting of Ti, Fe, Mn, Co, Ni, Mo, W, In, and Sn; (b) one or more metals selected from the group consisting of Ti, Fe, Co, Mg, Al, Ga, In, and Sn,; and (c) one or more metaloid selected from the group consisting of B, Si, Ge, and Sb.
The invention includes certain novel features and a combination of parts hereinafter fully described, illustrated in the accompanying drawings, and particularly pointed out in various aspects of the invention, it being understood that various changes in the details may be made without departing from the spirit, or sacrificing any of the advantages of the described invention.
a-d) depicts transmission electron micrographs of Sn nanocrystals coated on the surface of carbon spheres at various magnifications.
a) Powder X-ray diffraction patterns of as-prepared Sn—Sb on the carbon sphere particles of
This invention relates to novel electrode materials for lithium electrochemical cells, to novel methods of preparing the electrode materials for electrochemical energy storage devices, such as electrochemical cells, batteries, supercapacitors and fuel cells incorporating such materials. The methods have particular application in the fabrication of electrode materials for lithium batteries, more specifically rechargeable lithium-ion batteries. Over recent years, in addition to the efforts that have been made to improve, for example, the electrochemical performance of micron-sized particles by tailoring the morphological properties of primary and secondary particles. There has also been increased interest in fabricating electrode particles that are stable at the nano-sized level, such as lithium-iron-phosphate LiFePO4 (olivine) cathodes and lithium titanate Li4Ti5O12 (spinel) anodes, see for example, J.-M. Tarascon and M. Armand, Nature, volume 414, page 359 (2003). Such materials can be beneficial to improving the capacity, energy and power of lithium batteries rate and cycle life.
Several techniques have been developed over the years to fabricate nanomaterials for battery electrodes, for example, those involving hydrolysis, oxidation, solid-state, solvothermal, chemical-vapor-deposition, sonochemical, microwave irradiation, aerosol spray pyrolysis, inert gas condensation, high-energy ball milling, thermolysis, plasma synthesis, electrodeposition, and sol-gel reactions. These processes can be used to synthesize nanomaterials to varying degrees of commercially-viable quantities. Additionally, nanomaterials can be coated to increase the thermal, mechanical and/or chemical stability of materials, increase their durability and lifetime, decrease friction, inhibit corrosion, prevent aggregation, thereby modifying their overall physicochemical properties.
Considering the advantages and disadvantages of the known methods and the requirement of today's nanotechnology, a facile synthetic approach using an autogenic process reactor to prepare new electrode materials for energy storage applications has been developed. An autogenic pressure reactor system was first described by Pol et al., for example, in Chemistry of Materials, Volume 16, page 1793 (2004) for the stabilization of ZrO2 nanoparticles for their possible application as a catalyst or a catalyst support for various gas-phase reactions. The method makes use of a reactor in which one or more chemical precursors (either solid or liquid) are dissociated without addition of solvents and reacted in an enclosed chamber at elevated temperature, thereby creating self-generated pressure within the chamber. Reaction parameters such as heating rate, temperature, time, reactant concentration, stoichiometry, pressure, and atmosphere (either oxidizing, reducing or inert) can be controlled to fabricate a wide range of materials with various morphologies, particle shape and size, with either nano- or micron sized dimensions.
Odoni et al. used an autogenic pressure reactor for making a precursor of carbon-coated V2O5 electrode particles for lithium cells, as disclosed in Advanced Materials, Volume 18, page 1431 (2006). For this reported experiment, a vanadium triethylate VO(OC2H5)3 precursor and a small scale, 2-5 cm3 volume stainless steel reactor was used. This experiment, however, had several limitations: (1) instead of forming the desired carbon-coated V2O5 product, a reduced carbon-coated V2O3 product was formed; (2) an oxidation step was required to convert the V2O3 product to V2O5 at 300° C. or higher in air; and 3) the reactors were limited to an upper maximum reaction temperature of 700° C. and by an inability to accurately control the reaction atmosphere and pressure to ensure safety against possible venting and explosion.
The inventors have subsequently discovered that autogenic reactions can produce, in situ, a variety of unique ‘core-shell’ materials, for example, those with a metal, metal alloy, metalloid, metal oxide, metal phosphate or metal silicate core and an outer shell, coating or environment, for example, a carbon shell, coating or environment providing improved electronic and/or ionic conductivity on and between electrode particles, which can be particularly important when insulating anode and cathode products, such as TiO2 and LiFePO4, are fabricated. If, however, the outer shell of the core electrode acts as an electronic insulator and conducts Li+ions, then the shell can act advantageously as a solid electrolyte layer to protect the electrochemically active electrode core from undesired reactions at the particle surface. It has also been discovered that a wide range of novel products with unique morphologies can be produced by autogenic reactions and that the formation of a desired product is highly dependent on the identification and selection of the precursor materials. In particular, it has been discovered that this technique can be used selectively and effectively to prepare some electrode materials for lithium batteries directly within the reaction chamber with insignificant or no side reaction products. A particularly significant discovery is that carbon spheres, carbon nanotubes and other rounded carbon shapes, such as prolate shapes, can be prepared by autogenic reactions and that improved electrochemical performance of the carbon electrodes with respect to their reactivity with lithium can be obtained by heating the carbon products of autogenic reactions to elevated temperatures, for example above 1000° C., and preferably above 2000° C., without destroying the overall morphology of the carbon. The products of autogenic reactions are highly dependent on the identification and selection of the precursors and the reactions conditions under which the products are synthesized.
The materials produced by the autogenic reactor have particular application in primary and secondary (rechargeable) batteries, including, for example, lithium polymer batteries, lithium sulfur batteries and, most notably, lithium-ion batteries that are used for powering a broad range of devices, such as portable electronics (cell phones and laptop computers), medical, space, aeronautical and defense-related devices, as well as hybrid-electric, plug-in hybrid-electric, and all-electric vehicles.
In one embodiment of the present invention, a lithium- or lithium-ion electrochemical cell comprises a cathode, an anode, and a non-aqueous lithium-containing electrolyte therebetween wherein one or more of the anode and/or the cathode comprises at least one particulate carbon-containing material selected from the group consisting of one or more carbon-containing metal oxide or sulfide particles, the metal oxides or sulfides comprising one or more ions of Ti, Fe, Mn, Co, Ni, Mo, W, In, and Sn optionally with Li ions, carbon-containing metal particles comprising one or more of Ti, Fe, Co, Mg, Al, Ga, In, and Sn (preferably metals that alloy with Li such as Mg, Al, Ga, In, and Sn), carbon-containing metalloid particles comprising one or more of B, Si, Ge and Sb that alloy with Li, or carbon-containing metal phosphate particles, the metal phosphates comprising one or more ions of Ti, V, Mn, Ni, and Co, optionally with Li ions, or rounded carbon particles including, but not limited to, carbon spheres, prolate-shaped spheroids, oblate-shaped spheroids, and carbon nanotubes. In principle, from the description above, the carbon material of this invention can be construed as forming carbon-composites with the metal oxide-, metal-, metalloid particles, preferably formed by depositing the metal oxide, metal and/or metalloid particles on the surface of the carbon material. The carbon material of this invention can, in principle, be one or more of any form of carbon known in the art, such as graphitic carbon, disordered or ‘hard’ carbons, and the like, including rounded carbon shapes such as spherical carbon, carbon prolate spheroids, carbon and carbon nanotubes, and the like. The invention includes carbon-containing materials that are stoichiometric, defect or disordered with respect to their composition and atomic, cationic or anionic sites. In a preferred embodiment, the particulate carbon-containing material is prepared by reacting one or more solid or liquid, solvent-free chemical precursor materials comprising the elements making up the material in an enclosed autogenic pressure reactor in which the precursor materials are dissociated and reacted at elevated temperature, thereby creating self-generated pressure within the reactor. Preferably, the reactor operates under conditions ranging from a minimum working pressure of about 100 pounds per square inch and a minimum temperature of about 100° C., to a maximum working pressure in the range of about 800 to about 2000 pounds per square inch, typically about 400 to about 1000 pounds per square inch, and a maximum temperature in the range of about 300 to about 800° C., typically about 500 to about 800° C. In a particular embodiment, the anode and/or the cathode comprises at least one particulate carbon-containing material consisting of one or more carbon-containing metal oxide particles, carbon-containing metal sulfide particles, carbon-containing metal particles or carbon-containing metalloid particles as described above, can be fabricated, for example, by depositing the metal oxide, metal sulfide, metal and/or metalloid particles, preferably nanoparticles, on the surface of the carbon material such as rounded carbon spheres, carbon prolate spheroids, carbon nanotubes and the like. In a specific example, the metal oxide, metal and/or metalloid particles can be deposited by sonochemical methods, after the carbon products had first been synthesized by autogenic reactions in accordance with the principles of this invention, as described more fully in Examples 6 and 7.
In a preferred embodiment, the particulate carbon-containing material is a carbon-coated metal oxide or metal phosphate nanoparticulate material comprising particles having a titanium oxide core, a tin oxide core, or a lithium-metal-phosphate core such as an olivine-type core or a Nasicon-type core, which are coated with about 0.5 to about 30 percent by weight of carbon, the particles having a size in the range of about 5 to about 150 nm. The metal of the metal oxide, metal sulfide, or metal phosphate comprises one or more metals selected preferably from the group consisting of V, Ti, Fe, Mn, Ni, and Co. The carbon-coated metal oxide, metal sulfide, or metal phosphate nanoparticle materials are prepared via an autogenic pressure reaction, as described above.
In one preferred embodiment, the carbon-coated metal oxide nanoparticle material comprises, for example, titanium dioxide core particles coated with about 0.5 to about 30 percent by weight of carbon. The nanoparticle material has a size in the range of about 5 to about 150 nm, and the titanium dioxide core particles are predominately single phase anatase TiO2. The titanium dioxide material can be prepared by reacting one or more solid, solvent-free titanium carboxylate precursor materials (e.g., titanium (IV) oxyacetyl acetonate) in an autogenic pressure reaction, as described herein. Optionally, the product of the autogenic pressure reaction can be heated in air to reduce the amount of carbon coating the product. Other titanium oxide materials, such as those with a rutile-type structure, TiO2—B structure and amorphous titanium oxide are known in the art. All such TiO2 materials are useful as anode materials in lithium electrochemical cells, particularly if fabricated with nano dimensions, typically, but not exclusively, less than 100 nm.
In another preferred embodiment, the particulate carbon-containing material comprises MoO2 nanoparticles coated with carbon, or alternatively, when heated in air, to convert the molybdenum oxide core to MoO3, while maintaining a residual shell of carbon around the oxidized core.
In another preferred embodiment, the carbon-coated metal oxide particle material comprises metal oxide core nanoparticles, such as tin dioxide particles having a size in the range of about 5 to about 100 nm, coated with about 1 to about 4 nm of carbon. The tin dioxide core particles are predominately cassiterite-type SnO2. The tin dioxide material can be prepared by reacting one or more solid, solvent-free tin alkoxide precursor materials (e.g., tin (II) ethoxide) in an autogenic pressure reaction as described herein. Optionally, the product obtained from the autogenic pressure reaction can be heated in air to reduce the amount of carbon coating the product or it can be heated in a reducing atmosphere such as nitrogen or dilute hydrogen to reduce the tin dioxide, such that carbon coated SnO2-x(0<x≦2) materials, including defect tin oxide materials and metallic Sn are formed. Such materials are useful as anode materials in electrochemical cells.
In yet another preferred embodiment, the particulate carbon-containing material comprises a carbon-coated metal phosphate nanoparticulate material comprising core particles, for example, having an olivine-type structure or a Nasicon-type structure coated with about 0.5 to about 30 percent by weight of carbon, the nanoparticulate material having a particle size in the range of about 5 to about 150 nm, and wherein metal ions in the olivine or Nasicon-type structure comprises one or more metals selected preferably from the group consisting of V, Ti, Fe, Mn, Ni and Co. Such phosphate materials are useful as cathode materials as well as solid electrolyte materials, for example, on the surface of metal oxide cathode particles in electrochemical cells.
The carbon-coated metal phosphate nanoparticulate materials can be prepared by reacting one or more solid, solvent-free precursor materials in an autogenic pressure reaction as described herein. The precursor materials include one or more compounds comprising carbon, phosphate, Li, and a metal selected preferably from V, Ti, Fe, Mn, Ni or Co. Optionally the carbon-coated olivine product obtained from the autogenic pressure reaction can be heated in air to reduce the amount of carbon coating the product. Examples of suitable precursor materials for fabricating LiMPO4 olivine-type materials include one, or a combination, of a Fe, Mn, Ni or Co carboxylate and a lithium phosphate salt or one, or a combination, of a Fe, Mn, Ni or Co phosphate and a lithium carbonate salt.
In another preferred embodiment, the particulate carbon-containing material comprises carbon microspheres comprising generally spherical carbon particles. The size of the spherical carbon particles can vary, for example, in the range of about 1 to about 5 microns in diameter, when made by selected reactor conditions of temperature and pressure as described hereafter. The carbon microspheres can be prepared, for example, by reacting a solvent-free polyethylene terephthalate polymer in an autogenic pressure reaction as described herein. Other precursor materials, such as mesityline and other polymers, are possible and can be used instead of the polyethylene terephthalate polymer to produce the carbon spheres. Preferably, the carbon microspheres can contain a combination of disordered carbon and graphitic carbon. The ratio of disordered carbon to graphitic carbon can be greater than 1, for example, in the range of about 1 to about 1.1, or it can be less than 1 (e.g., if the microspheres subsequently are heated in under inert conditions, for example under vacuum or under an inert gas, such as He or Ar, at a temperature of about 1000 to about 3000° C. to increase the graphitic character within the spheres), which can be advantageous for stability, capacity and rate reasons. The invention extends to include carbon products, made by autogenic reactions, with other rounded shapes, such as prolate shapes, oblate shapes and the like, and particularly to heated products that have been discovered to exhibit remarkable morphological stability not only when subjected to high temperature but also to their reaction with lithium, unlike the as-prepared rounded carbon particles that are not subjected to a subsequent heat treatment process.
In other preferred embodiments, the carbon-containing material comprises carbon nanotubes. These nanotubes can be prepared, for example, by reacting solvent-free precursor materials comprising low density polyethylene and a cobalt carboxylate compound, the latter compound forming a cobalt catalyst during the autogenic pressure reaction as described herein. The carbon nanotubes can optionally include nanoparticles of other electrochemically active anode materials, for example, titanium dioxide, silicon, tin or a combination thereof on the surface of the nanotubes or in close contact with the nanotubes. The invention extends to include heat-treated nanotubes that are subjected in a second step to higher temperatures of about 1000 to about 3000° C. under inert conditions, for example, under vacuum or under an inert gas, such as He or Ar, as described hereinbefore for the rounded carbon products.
The present invention also provides a battery comprising a plurality of electrochemical cells as described herein arranged in parallel, in series, or both.
In yet a further embodiment, the invention relates to a scaled-up reactor design, particularly for laboratory research, with a volumetric capacity of 20 ml or more, preferably 40 ml or more, that can operate at a minimum working pressure of about 100 pounds per square inch and a minimum temperature of about 100° C., and a maximum working pressure of about 2000 pounds per square inch and a maximum temperature of about 800° C. to produce the electrode and electrolyte materials of this invention. It stands to reason that higher volumetric capacities will be required for pilot plant- or industrial-scale production. Preferably, the reactor is capable of operating at a minimum working pressure of about 100 pounds per square inch and a minimum temperature of about 100° C., and a maximum working pressure of about 1200 pounds per square inch and a maximum temperature of about 600° C. Most preferably the reactor is capable of operating at a minimum working pressure of about 100 pounds per square inch and a minimum temperature of about 100° C. and a maximum working pressure of about 800 pounds per square inch and a maximum temperature of about 300° C. The design of the autogenic process reactor consists of a suitable reaction vessel, such as a Haynes 230 alloy reactor, a heating furnace with programmable temperature control, an ability to purge desired gases, and a supporting stand assembly as shown in
The syntheses of battery electrode and electrolyte materials are carried out with the autogenic reactor typically as follows. Appropriate amounts of the chemical precursors, preferably comprised of one or more organic or organometallic precursor materials, optionally in combination with other decomposable inorganic precursor materials that will define the stoichiometry of the final product are placed in a ceramic tube, which is then introduced into the reaction vessel. The reactor is sealed using a high temperature graphite gasket, and thereafter heated at a rate of about 1 to about 80° C. per minute, preferably about 10 to 40° C. per minute to the desired temperature (about 100-800° C.). The reaction vessel is then held at elevated temperature depending upon the reaction requirements that typically range from about 1 minute to about 3 hours, or longer if required. Chemical dissociation and transformation reactions take place under the autogenic pressure of the precursor to yield one or more reaction products, such as a metal, a metal alloy or intermetallic compound, a metalloid, a metal oxide, a metal phosphate, a metal silicate, mixed metal variations thereof, and carbon. For example, the metal, intermetallic and metalloid products can be Sn, Cu6Sn5 and Si, whereas metal oxide or sulfide products can be transition metal oxides or sulfides, selected preferably from Ti, Fe, Mn, Ni, and Co and optionally with Li, such as TiO2, Li4Ti5O12, TiS2, or oxides of the main group metal elements, such as SnO2. The products can therefore be lithium-containing metal oxides or sulfides such as those having layered and spinel structures as known in the art. The carbon products can be comprised of amorphous carbon, hard carbon, graphitic carbon, carbon nanotubes and combinations thereof, particularly those with rounded morphologies and shapes, such as spherical carbon particles, or those with prolate or oblate shapes. In a particular embodiment, the invention relates to an autogenic method of fabricating rounded carbon particles for an electrochemical cell, comprising carbon spheres, prolate-shaped spheroids, oblate-shaped spheroids, and carbon nanotubes or modifications thereof that includes heating the product of the autogenic reaction under inert conditions to a temperature between 1000 to 3000° C. The metal phosphates can be lithium metal phosphates, such as LiFePO4 and those with a Nasicon-type structure; likewise, the metal silicates include the family of known lithium metal silicate compositions and structures. The vessel is then cooled to room temperature. During the autogenic reaction, the organic components of the precursors decompose to generate gases such as CO, H2O and hydrocarbons, and further reduction can take place that can result in carbon coatings on the electrode particles or carbon products. The pressure can be released during the autogenic reaction, and the reaction atmosphere controlled to control the composition of the final product. For example, during the above-mentioned thermal dissociation reaction, the pressure in the closed reaction vessel can increase up to 1000 psi or more. To monitor and control the autogenic pressure, the reactor is equipped with safety protection devices such as pressure gauges, dual thermocouples, and a gas release capability. When cooling to room temperature, the pressure in the reactor decreases close to atmospheric pressure; the remaining pressure is carefully released using the gas release valve prior to opening. During operation, and during opening, the reactor is positioned behind a blast shield for safety.
In a further embodiment, autogenic reactions can be used to prepare electronically conducting coatings or layers, or ionically conducting coatings or layers, or both ionic and electronic coatings or layers on pre-existing core materials within an autogenic reactor. For example, carbon-containing materials can be fabricated by autogenic reactions on lithium metal oxide cathode core materials within an autogenic reactor to provide enhanced electronic conductivity and to protect the lithium metal oxide electrodes from undesired side reactions during charge or discharge at high potentials, for example >4.2 V vs. metallic lithium. Alternatively, ionically-conducting coatings or layers of non-carbon-containing materials, such as coatings or layers comprising lithium metal aluminates, lithium metal silicates, lithium metal phosphates, lithium metal zirconates and the like, can be deposited on the surface of pre-existing core materials within an autogenic reactor to provide enhanced ionic conductivity and to protect the electrodes from undesired side reactions from during charge or discharge at high or low potentials vs. metallic lithium.
The following examples describe the principles of the invention as contemplated by the inventors, but they are not to be construed as limiting examples. The examples demonstrate, in particular, the versatility of autogenic reactions in synthesizing materials with a diverse range of particle morphologies, conducive to their use as electrodes and/or current collecting media for lithium battery applications.
Carbon-coated TiO2 was directly prepared from a single solid precursor, titanium (IV) oxyacetyl acetonate, TiO[C5H8O2]2. The precursor was introduced into the closed autogenic pressure reactor in an inert nitrogen atmosphere and heated at about 30° C./minute to about 700° C. for about 1 hour. The furnace was then turned off and the reactor was cooled for about 3 hours. Scanning-electron-microscope (SEM) images (
Carbon analysis revealed that the as-prepared TiO2 product contained about 30% carbon by weight. The product was further heated in air at about 450° C. for about 1 hour to reduce the amount the carbon, leaving a thin layer of carbon around the TiO2 nanoparticles. A thermogravimetric analysis (TGA) of the heated product showed that approximately 5% by weight of carbon remained in the sample. Thus the amount of carbon in such coated electrodes can be tailored to ensure optimum electrode loading and electrochemical performance.
Electrochemical evaluations were carried out in coin cells using a lithium metal foil electrode, the carbon-coated TiO2 electrode under investigation, and an electrolyte consisting of 1.2M LiPF6 in a 3:7 mixture of ethylene carbonate (EC) and ethylmethyl carbonate (EMC) (Tomiyama). The working electrode consisted of about 85 wt % of carbon-coated-TiO2 powder, about 8 wt % carbon, and about 7 wt % polyvinylidene difluoride (PVDF) binder on carbon-coated aluminum foil. For the cycling experiments, cells were galvanostatically charged and discharged over a range of about 1.1 to about 2.35 V at about 0.1 mA/cm2 (a C/17 rate). The electrochemical charge/discharge profiles and capacity vs. cycle number plot of a Li/carbon-coated TiO2 cell, highlight the reversibility of the carbon-coated TiO2 electrode, are shown in
In addition to electronically-conductive carbon coatings, this invention can be extended to include ionically-conducting solid electrolyte coatings, such as Li+-ion conducting solid electrolyte coatings on electrode particles and may be comprised, for example, of one or more inorganic materials selected from the family of lithium metal oxides, lithium metal phosphates, lithium metal silicates and the like. The invention therefore includes electrode materials that contain an outer shell or coating comprised of conductive carbon layer or a lithium-ion conducting solid electrolyte layer, or a combination of both.
Carbon-coated MoO2 nanoparticles coated were prepared by the autogenic reaction of a single precursor, bis(acetylacetonato)-dioxomolybdenum (VI), (C5H8O2)2MoO2 at 700° C. X-ray diffraction and Raman spectroscopy measurements identified the product as highly pure, crystalline monoclinic form of MoO2. The carbon coating was essentially amorphous to X-rays (confirmed by Raman spectroscopy), providing electronic conductivity to the core oxide electrode particles. The highly crystalline character of MoO2 particles was clearly evident in the high-resolution image of the product as shown in
The electrochemical properties of carbon coated MoO2 and MoO3 electrodes were determined in lithium half cells (coin-type, size 2032) using a lithium foil counter electrode. The MoO2—C electrode was prepared by coating a slurry consisting of about 80 wt % MoO2—C, 10% carbon black and about 10 wt % PVDF as binder on a copper foil. The MoO3—C electrode was prepared in a similar fashion. Both electrodes were dried under vacuum for about 10 hours at about 80° C. The electrolyte was a 1.2 M solution of LiPF6 in a 3:7 (by volume) solvent mixture of ethylene carbonate (EC) and ethylmethyl carbonate (EMC). The cells were assembled in a He-filled glove box. Cells were charged and discharged galvanostatically at room temperature at about 3.0 V to about 0.005 V at a C/6 rate.
A single Sn(OC2H5)2 precursor, when dissociated in the closed autogenic pressure reactor at about 600° C. under air for about 3 hours yielded carbon-coated SnO2 electrode particles. The primary SnO2 particles representing the core were typically about 10-15 nm in dimension and surrounded by about 2-3 nm of semi-graphitic carbon (
Carbon-coated or carbon-containing lithium-metal-phosphates with the olivine-type structure, such as LiFePO4, LiNiPO4, LiCoPO4, LiMnPO4 were fabricated with the autogenic pressure reactor. Oxalates or acetates of Fe, Co, Ni and Mn were initially ball-milled with LiH2PO4 for 1 hour and then reacted in the autogenic pressure reactor under nitrogen at about 600-700° C. for a further about 1 hour. When LiFePO4 was prepared by this method, the product consisted of spherical particles on average less than about 100 nm in diameter (
Carbon-coated LiFePO4 could also be prepared by reacting FePO4 with Li2CO3 in the presence of glucose in an autogenic reaction in an inert nitrogen atmosphere. The electrochemical performance of such carbon-coated LiFePO4 electrodes in a Li/LiFePO4 coin cell, constructed in a similar manner as described in Example 1, is shown in
Spherical carbon particles were prepared by the thermal decomposition of about 2 grams of polyethylene based polymer (waste plastic containing hydrocarbons) in an enclosed, but ventable, 10 mL Haynes 230 alloy autoclave reactor under nitrogen.
The thermal decomposition of 2 grams of polyethylene terephthalate polymer in a closed reactor under autogenic (self generating) pressure yielded solid carbon microspheres, approximately 1-5 μm in diameter, as illustrated in the scanning electron microscope images in
Corresponding images of carbon spheres that had been heated at about 2400° C. for about 1 hour in an inert atmosphere are provided in
The electrochemical properties of carbon sphere electrodes were determined in lithium half cells (coin-type, size 2032) using a lithium foil counter electrode. The carbon electrodes were prepared by coating a slurry consisting of about 92 wt % active carbon spheres and about 8 wt % PVDF as binder on a copper foil. Both electrodes were dried under vacuum for about 12 hours at about 80° C. The electrolyte was a 1.2 M solution of LiPF6 in a 3:7 (by volume) solvent mixture of ethylene carbonate (EC) and ethylmethyl carbonate (EMC). The cells were assembled in a He-filled glove box. Cells were charged and discharged galvanostatically at room temperature at about 1.5 to about 0.005 V at a current density of about 0.25 mA/g.
In general, the capacity delivered by both as-prepared carbon sphere and the heated carbon sphere electrodes, their cycling profiles, and cycling stability was similar (
Furthermore, the carbon spheres were heated at about 2800° C. for about 1 hour in an inert atmosphere, the product being shown in
The increase in graphitic order on heating the carbon spheres to higher temperature was also evident from the powder X-ray diffraction pattern (
The electrochemical properties of carbon sphere electrode particles that had been heated at 2800° C. were determined in lithium half cells (coin-type, size 2032) using a lithium foil counter electrode. The cells were assembled in a He-filled glove box. Cells were charged and discharged galvanostatically at room temperature at about 1.5 to about 0.005 V at a current density of about 0.25 mA/g.
The electrochemical properties of carbon sphere electrodes (heat-treated at 2800° C.) were also evaluated in lithium-ion full cells (against a high-capacity 0.5Li2MnO3.0.5LiNi0.44Co0.25Mn0.31O2) counter electrode. The initial two discharge/charge curves of a cathode-limited cell comprising with a positive electrode comprising carbon spheres and 0.5Li2MnO3.0.5LiNi0.44Co0.25Mn0.31O2, cycled between 2 and 4.6 V at a constant current density of 100 mA/g (about C/3 rate), as well as the corresponding capacity vs. cycle number plot, are provided in
In a specific embodiment, the carbon products of this invention can be decorated, coated, or combined with metal oxide, metal, or metalloid particles as hereinbefore described to enhance the electrochemical properties of the carbon electrode materials, for example, with SnO2, Sn, Sb, and/or Si nanoparticles to enhance the specific capacity of carbon sphere electrodes, as described below.
To further enhance their electrochemical properties, carbon microspheres, heated at about 2400° C. for about one hour (
The morphology of sonochemically-coated SnCl(OH) molecules on carbon spheres and a heat-treated carbon sphere-Sn product are shown in
The powder X-ray diffraction pattern of the SnCl(OH)-coated spheres showed only carbon diffraction peaks, indicating that the Sn-containing particles (
Electrochemical evaluations were carried out in coin cells using a lithium metal foil electrode, a Sn-carbon sphere counter electrode, and an electrolyte consisting of 1.2M LiPF6 in a 3:7 mixture of ethylene carbonate (EC) and ethylmethyl carbonate (EMC) (Tomiyama). The cells were assembled in an argon-filled glove box. The working electrodes were prepared by mixing the Sn-carbon sphere powder, SUPER P® conductive carbon black (Timcal Graphite and Carbon (Bodio, Switzerland), and polyvinyldifluoride (PVDF) binder in a weight ratio of 80:10:10, which was then pasted onto a pure Cu foil and dried by conventional methods. For the cycling experiments, cells were galvanostatically charged and discharged between 1.5 and 0.01 V at a current density of 136 mA/g. The electrochemical discharge/charge profiles and capacity vs. cycle number plot and the rate studies of a Li/Sn-carbon sphere cell, highlight the reversibility of the Sn-carbon sphere electrode, as shown in
It is well known that tin extensively forms alloys with lithium to form a series of binary compounds, the end-member having the composition of approximately Li22Sn5, which has a theoretical capacity of 991 mAh/g. When tin alone is used (i.e., not coated onto carbon), although showing a large initial discharge capacity, it loses capacity rapidly on cycling due to the cracking and crumbling of the material as a result of the large volume expansion and contraction that occurs during electrochemical cycling. The Sn-carbon sphere electrodes of this invention, particularly when synthesized by sonochemical processes demonstrate stable cycling in the potential range 1.5 to 0.01 V vs. Li.
In another example, a mixture of electrochemically active SnO2 and Sb nanocrystals were decorated on the surface of carbon sphere electrode particles. To synthesize these materials, about 0.7 grams of as-prepared carbon spheres (i.e., those shown in
The powder X-ray diffraction patterns of the as-prepared SnO2—Sb coated carbon spheres showed that the coating was essentially amorphous to X-rays (
The morphology of the carbon spheres that had been sonochemically-treated with SnCl2 and SbCl3 is shown in
Electrochemical evaluations of carbon sphere-SnO2/Sb composite electrodes were carried out in coin cells using a lithium metal foil counter electrode and an electrolyte consisting of 1.2M LiPF6 in a 3:7 mixture of ethylene carbonate (EC) and ethylmethyl carbonate (EMC) (Tomiyama). The cells were assembled in an argon-filled glove box. The working electrodes were prepared by mixing carbon sphere-SnO2/Sb powder, SUPER P® conductive carbon black, and poly(vinylidinedifluoride) (PVDF) binder in a weight ratio of 80:10:10 and pasting the mixture with N-methyl-pyrrolidinone (NMP) onto a pure Cu foil. For the cycling experiments, cells were galvanostatically charged and discharged between about 1.5 and about 0.01 V at a current density of about 136 mA/g. The electrochemical charge/discharge profiles, capacity vs. cycle number plot and rate data of a Li/carbon sphere-SnO2/Sb cell, highlight the reversibility of the carbon sphere-SnO2/Sb electrode, as shown in
a) shows the discharge/charge behavior of a Li/carbon sphere-SnO2/Sb cell during the first two cycles at a current density of 75 mA/g (about C/5.5 rate) when cycled between 1.5 and 0.01 V). The first-cycle discharge and charge capacities of SnO2/Sb-carbon spheres composite electrode are 612 mAh/g and 394 mAh/g, respectively. The first cycle irreversible capacity loss is about 35%. A steady reversible capacity of 425 mAh/g with C/2.7 rate for 40 cycles is shown in the capacity vs. cycle number plot (
The synthesis of prolate-shaped carbon particles was carried out by a controlled autogenic reaction of refined corn oil at about 700° C. under an autogenic pressure of about 4.2 MPa. The scanning electron micrographs (
The Raman spectrum of the as-prepared carbon particles with a prolate shape (
The electrochemical properties of the prolate-shaped carbon electrodes were determined in lithium half cells (coin-type, size 2032) using a lithium foil counter electrode. The carbon electrodes were prepared by coating a slurry consisting of about 72 wt % of the prolate-shaped carbon particles, 12 wt % carbon black and about 16 wt. % polyvinylidine-difluoride (PVDF) as binder on a copper foil that acted as a current collecting substrate. The as-prepared electrode was dried under vacuum for about 10 hours at about 80° C. The electrolyte was a 1.2 M solution of LiPF6 in a 3:7 (by volume) solvent mixture of ethylene carbonate (EC) and ethylmethyl carbonate (EMC). The cells were assembled in a He-filled glove box. Cells were discharged and charged galvanostatically at room temperature at about 2 to 0.005 V at a current density of about 40 mA/g.
The carbon materials of this invention also have application in other types of lithium cells, for example, as current collectors in the cathodes of lithium-polymer and lithium-sulfur cells.
Unlike the spherical carbon electrode morphology that was created by the thermal decomposition of polyethylene terepthalate polymer at in the autogenic pressure reactor, as described in Example 4 above, it was discovered that a carbon nanotube electrode morphology could be created by the thermal decomposition of low density polyethylene containing about 20 wt % of a cobalt acetate catalyst in the autogenic pressure reactor under a nitrogen atmosphere at about 700° C. for about 2 hours (
The electrochemical behavior of a Li/carbon nanotube half cell, constructed in the same manner as the cell described in Example 3, is shown in
The carbon nanotubes prepared in Example 6 were used as a template for depositing nanoparticulate TiO2 and Si to create carbon nanotube—TiO2 and carbon nanotube—Si ‘hybrid’ electrode materials in which the carbon nanotube component provided not only electrochemical capacity to the electrode but also electrical connectivity between the electroactive, nanoparticulate TiO2 and Si components. For example, about 1.3 g of a titanium precursor, (C5H8O2)2TiO, was dissolved in about 20 ml of water. The aqueous solution was sonicated in a bath with the addition of about 130 mg of carbon nanotubes. After about 20 minutes of ultrasonication, the water was evaporated and the resultant dry powder heated in the autogenic pressure reactor at about 400° C. in an air atmosphere for about 2 hours. The product of this reaction consisted of nanosized (<10 nm) titania particles that decorated the surfaces of the carbon nanotubes. Elemental mapping confirmed the presence of Ti, O and C throughout this nano-composite material. An analogous experiment was conducted whereby triethylsilane, (C2H5)3SiH, was decomposed in presence of pre-prepared carbon nanotubes in the autogenic pressure reactor in an inert argon atmosphere at approximately about 650° C. for about 2 hours to decorate the surface of the carbon nanotubes with nano-sized Si particles. By analogy to the materials prepared by autogenic reactions, as described hereinbefore, such products have application as anode and current collecting materials in lithium cells and batteries.
This invention extends to the use of a relatively inexpensive and environmentally-friendly catalyst, ferrocene, as an alternative to cobalt acetate catalyst during the synthesis of carbon nanotubes by autogenic reactions. This autogenic pyrolysis process from solid-state precursors involves the heating of low density polyethylene in a sealed chamber to 700° C., where carbon and hydrogen atoms separate to form carbon structures and hydrogen gas. Conventional production of carbon nanotubes requires input of hydrogen and ethylene gases derived from fossil fuels, whereas the autogenic process, as described hereinbefore, can use plastic waste as a precursor. The addition of ferrocene (about 20 wt %) catalyst during the thermolysis of low density polyethylene (80 wt %), creates approximately 900 psi pressure during the autogenic reaction when carbon nanotubes several microns long but less than 60 nm wide are produced (
The powder X-ray diffraction patterns of the Fe-encapsulated carbon nanotubes showed evidence of carbon, iron and iron carbide (Fe3C) (
The electrochemical performance of a Li/Fe-encapsulated carbon nanotube cell, constructed in the same manner as the cell described in Example 3, is shown in
Whereas this specification and the examples provided therein pertain specifically to electrode materials for non-aqueous lithium cells and batteries, including lithium ion, lithium-polymer, lithium-sulfur cells and batteries, it will be obvious to those skilled in the art that the invention pertains also to electrode materials for cells and batteries using aqueous electrolytes, such as alkaline Zn/MnO2 and nickel-metal hydride cells and batteries, as well as to other energy storage devices such as supercapacitors with either aqueous or non-aqueous electrolytes and fuel cells.
This invention, therefore, relates to a method for synthesizing variety of materials using an autogenic process reactor for electrochemical energy storage electrodes, such as those used in an electrochemical cell, shown schematically in
The use of the terms “a” and “an” and “the” and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to,”) unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.
This application is a continuation in part of U.S. application Ser. No. 12/915,395, filed on Oct. 29, 2010, which claims the benefit of U.S. Provisional Application Ser. No. 61/360,027, filed on Jun. 30, 2010, and of U.S. Provisional Application Ser. No. 61/280,025, filed on Oct. 29, 2009, each of which is incorporated herein by reference in its entirety.
The United States Government has rights in this invention pursuant to Contract No. DE-AC02-06CH11357 between the United States Government and UChicago Argonne, LLC representing Argonne National Laboratory.
Number | Date | Country | |
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61360027 | Jun 2010 | US | |
61280025 | Oct 2009 | US |
Number | Date | Country | |
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Parent | 12915395 | Oct 2010 | US |
Child | 13454553 | US |